Organic photovoltaic cell and light emitting diode with an array of 3-dimensionally fabricated electrodes

ABSTRACT

Disclosed herein, in certain instances, is a novel photovoltaic cell that uses unique microarchitectural and multi-layer functional designs. Further disclosed herein, in certain instances, is a 3-dimensional electrode.

CROSS-REFERENCE

This application claims the benefit of U.S. Provisional Application No.61/059,995, entitled Feasibility Study of Low-Cost Polymeric andCarbon-Based Photovoltaic Cells, filed Jun. 9, 2008, the contents of theapplication are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

Solar energy is abundantly available in the environment and photovoltaiccells are the main devices to convert solar energy into electricity. Inthe US, about 6% of total energy is provided by renewable sources, ofwhich only 6% is attributable to solar cells.

SUMMARY OF THE INVENTION

Disclosed herein, in certain instances, is a novel photovoltaic cellthat uses micro-architectural and multi-layer functional designs.Currently, off-the-shelf silicon-based solar cell modules deliver energyefficiencies in the range of 15% with costs 30 cents to 40 cents per kWh(˜10 cents/kWh for grid-connected US electricity). The cells providedherein will offer an economic scale well below a target cost of about$4000/kWp, namely, under 20 cents/kWh if mass-produced, which is about50% of the cost of the state-of-the-art silicon-based photovoltaic cellsin current market.

Further disclosed herein, in certain instances, is a 3-dimensionalelectrode. As compared to traditional planar electrodes, thethree-dimensional electrode design disclosed herein increases thesurface contact areas (for example, by 3 to 6 times) for thickphotoactive layers without increasing the electrical resistance, andthus improving the energy conversion efficiency.

Disclosed herein, in certain instances, is a novel electroluminescentcell that uses unique micro-architectural and multi-layer functionaldesigns.

Further disclosed herein, in certain instances, is a 3-dimensionaldiode. As compared to traditional planar diodes, the three-dimensionalelectrode design disclosed herein increases surface area.

Disclosed herein, in certain embodiments, is a photovoltaic cellcomprising: (a) a plurality of three-dimensional electrodes comprising aconductive or semi-conductive or semi-conductive material, wherein theconductive or semi-conductive or semi-conductive material is selectedfrom: carbon, a carbon allotrope, or an organic polymer; and (b) atleast one photoactive material; wherein the shape of the electrodesvaries along the vertical axis. In some embodiments, the photovoltaiccell provides energy conversion efficiency of at least 5%, 7%, 10%, 15%,20%, 25%, 30%, 40%, or 50%. In some embodiments, at least some of thethree-dimensional electrodes are coated with a conductive polymer. Insome embodiments, the electrodes comprise anodes and cathodes and theanodes are selectively coated with the conductive polymer. In someembodiments, at least some of the anodes are coated with PEDOT:PSS. Insome embodiments, the cell further comprises two clear layers wherebythe electrodes and the photoactive material and sandwiched between thetwo clear layers. In some embodiments, electromagnetic radiation passesthrough at least two of the clear layers and at least a portion of saidelectromagnetic radiation is converted to energy. In some embodiments,the electromagnetic radiation is visible light. In some embodiments, aphoton from the electromagnetic radiation is absorbed by the photoactivematerial. In some embodiments, the photoactive material comprises adonor polymer and absorption of the photon excites an electron in thedonor polymer. In some embodiments, an excited electron migrates to thecathode creating a potential difference. In some embodiments, thediffusion length for migrating charges is less than 100 nm. In someembodiments, the three-dimensional electrodes form an array comprisinganodes and cathodes. In some embodiments, at least some of the anodeshave a work function of 5 eV or higher. In some embodiments, at leastsome of the cathodes have a work function of 5 eV or less. In someembodiments, at least some of the three-dimensional electrodes are inthe shape of a cylinder, a pyramid, a diamond, sphere, hemisphere, or arectangular prism. In some embodiments, the three-dimensional electrodesare in the shape of pyramids. In some embodiments, the three-dimensionalelectrodes are in the shape of cylinders. In some embodiments, theelectrodes are manufactured using a conductive or semi-conductive orsemi-conductive material that is subjected to a patterning process. Insome embodiments, the electrodes are manufactured using a conductive orsemi-conductive or semi-conductive material that is subjected to apatterning process selected from: stamping, extrusion, printing,lithography, rolling, or combinations thereof. In some embodiments, theelectrodes are manufactured using a conductive or semi-conductive orsemi-conductive material that is subjected to a patterning processfollowed by heating. In some embodiments, the electrodes aremanufactured using a conductive or semi-conductive or semi-conductivematerial that is subjected to a patterning process followed bysintering, pyrolysis, or baking. In some embodiments, the electrodes aremanufactured using a conductive or semi-conductive or semi-conductivematerial that is subjected to a patterning process followed bypyrolysis. In some embodiments, the electrodes are manufactured using aconductive or semi-conductive or semi-conductive material that issubjected to a patterning process followed by sintering. In someembodiments, the electrodes comprise graphite or glassy carbon. In someembodiments, the electrodes are arranged in a grouped pattern. In someembodiments, the electrodes are arranged in a separated pattern. In someembodiments, the electrodes are formed in a no trace architecture. Insome embodiments, at least some of the electrodes form a tracearchitecture. In some embodiments, at least some of the electrodes aretransparent. In some embodiments, at least some of the electrodes areporous. In some embodiments, the photoactive material surrounds at leastsome of the electrodes. In some embodiments, the photoactive materialcomprises a matrix of heterojunction photoactive material. In someembodiments, the photoactive material comprises crystalline silicone,cadmium telluride copper-indium selenide, copper indium/galliumdiselenide, ruthenium metalorganic dye, P3HT (poly(3-hexylthiophene)),PCBM (phenyl-C61-butyric acid methyl ester), or combinations thereof. Insome embodiments, the photoactive material comprises P3HT(poly(3-hexylthiophene)) and PCBM (phenyl-C61-butyric acid methylester). In some embodiments, the photoactive material comprises P3HT(poly(3-hexylthiophene)) and PCBM (phenyl-C61-butyric acid methyl ester)in a 1:1 ratio by weight. In some embodiments, the cell comprises afirst and a second photoactive material; and wherein the absorptionspectrum of the first photoactive material and the absorption of thesecond photoactive material are different. In some embodiments, thefirst and second photoactive materials are in defined layers. In someembodiments, the surface area of the photoactive material is increased,for example, by a factor of about 3 to about 6. In some embodiments, thecell further comprises a transparent material, wherein the transparentmaterial protects the cell from oxidation. In some embodiments, the cellfurther comprises a transparent material of glass, plastic, ceramic or acombination thereof. In some embodiments, the cell further comprises atransparent material of glass, wherein the glass protects the cell fromoxidation. In some embodiments, the cell further comprises a transparentmaterial of plastic, wherein the glass protects the cell from oxidation.In some embodiments, the cell is a solar cell. In some embodiments, thecell is used to make a solar panel.

Disclosed herein, in some embodiments, is a solar panel comprising aplurality of photovoltaic cells disclosed herein.

Disclosed herein, in certain embodiments, is a three dimensionalelectrode comprising a conductive or semi-conductive or semi-conductivematerial, wherein the conductive or semi-conductive material is selectedfrom: carbon, a carbon allotrope, or an organic polymer, and wherein theshape of the electrode varies along the vertical axis. In someembodiments, the three-dimensional electrode is coated with a conductivepolymer. In some embodiments, the electrode is a cathode. In someembodiments, the electrode is an anode and the anode is coated with theconductive polymer. In some embodiments, the anode is coated withPEDOT:PSS. In some embodiments, an anode has a work function of 5 eV orhigher. In some embodiments, a cathode has a work function of 5 eV orless. In some embodiments, the electrodes comprise a carbon material. Insome embodiments, the electrodes comprise graphite or glassy carbon. Insome embodiments, the electrode is in the shape of cylinder, a pyramid,a diamond, sphere, hemisphere, or a rectangular prism. In someembodiments, the electrode is in the shape of a pyramid. In someembodiments, the electrode is in the shape of a cylinder. In someembodiments, the electrode is manufactured using a conductive powderthat is subjected to a patterning process. In some embodiments, theelectrode is manufactured using a conductive or semi-conductive materialthat is subjected to a patterning process selected from: stamping,extrusion, printing, lithography, rolling, or combinations thereof. Insome embodiments, the electrode is manufactured using a conductive orsemi-conductive material that is subjected to a patterning processfollowed by heating. In some embodiments, the electrode is manufacturedusing a conductive or semi-conductive material that is subjected to apatterning process followed by sintering, pyrolysis, or baking. In someembodiments, the electrode is manufactured using a conductive polymerthat is subjected to a patterning process followed by pyrolysis. In someembodiments, the electrode is manufactured using a conductive powderthat is subjected to a patterning process followed by sintering. In someembodiments, at least some of the electrodes are porous.

Disclosed herein, in certain embodiments, is an electroluminescent cellcomprising: a plurality of three-dimensional diodes comprising aconductive or semi-conductive material, wherein the conductive orsemi-conductive material is selected from: carbon, a carbon allotrope,or an organic polymer; and a current source; wherein the shape of thediodes varies along the vertical axis, and wherein theelectroluminescent cell provides energy conversion efficiency of atleast 10%. In some embodiments, the photovoltaic cell provides energyconversion efficiency of at least 5%, 10%, 15%, 20%, 25%, 30%, 40%, or50%. In some embodiments, the diode comprises an anode and a cathode. Insome embodiments, the diode comprises a donor polymer and an acceptorpolymer. In some embodiments, at least a portion of the diodes is coatedwith a conductive polymer. In some embodiments, the anodes areselectively coated with the conductive polymer. In some embodiments, theanodes are coated with PEDOT:PSS. In some embodiments, the currentexcites electrons in the donor material. In some embodiments, theelectrons in the donor material combine with a hole. In someembodiments, the combining of an electron and a hole results in theelectron falling into a lower energy level. In some embodiments, anelectron falling into a lower energy level releases a photon. In someembodiments, the three-dimensional diodes form an array. In someembodiments, at least some of the three-dimensional diodes are in theshape of a cylinder, a pyramid, a diamond, sphere, hemisphere, or arectangular prism. In some embodiments, the three-dimensional diodes arein the shape of pyramids. In some embodiments, the three-dimensionaldiodes are in the shape of cylinders. In some embodiments, the diodesare manufactured using a conductive or semi-conductive material that issubjected to a patterning process. In some embodiments, the diodes aremanufactured using a conductive or semi-conductive material that issubjected to a patterning process selected from: stamping, extrusion,printing, lithography, rolling, or combinations thereof. In someembodiments, the electrodes are manufactured using a conductive orsemi-conductive material that is subjected to a patterning processfollowed by heating. In some embodiments, the diodes are manufacturedusing a conductive or semi-conductive material that is subjected to apatterning process followed by sintering, pyrolysis, or baking. In someembodiments, the diodes are manufactured using a conductive orsemi-conductive material that is subjected to a patterning processfollowed by pyrolysis. In some embodiments, the diodes are manufacturedusing a conductive or semi-conductive material that is subjected to apatterning process followed by sintering. In some embodiments, theelectrodes comprise graphite or glassy carbon. In some embodiments, thediodes are arranged in a grouped pattern. In some embodiments, thediodes are arranged in a separated pattern. In some embodiments, thediodes are formed in a no trace architecture. In some embodiments, thediodes form a trace architecture. In some embodiments, at least some ofthe diodes are transparent. In some embodiments, at least some of thediodes have a porous surface. In some embodiments, at least some of thediodes have a non-porous surface. In some embodiments, the cell furthercomprises a transparent material, wherein the transparent materialprotects the cell from oxidation. In some embodiments, the cell furthercomprises a transparent material of glass, plastic, ceramic or acombination thereof. In some embodiments, the cell further comprises atransparent material of glass, wherein the glass protects the cell fromoxidation. In some embodiments, the cell further comprises a transparentmaterial of plastic, wherein the glass protects the cell from oxidation.

Disclosed herein, in some embodiments, is a three dimensional diodecomprising a conductive or semi-conductive material, wherein theconductive or semi-conductive material is selected from: carbon, acarbon allotrope, or an organic polymer, and wherein the shape of thediode varies along the vertical axis. In some embodiments, at least aportion of the three-dimensional diode is coated with a conductivepolymer. In some embodiments, the diode comprises an anode and acathode. In some embodiments, the anode is coated with the conductivepolymer. In some embodiments, the anode is coated with PEDOT:PSS. Insome embodiments, the conductive or semi-conductive material is graphiteor glassy carbon. In some embodiments, the diode is in the shape of acylinder, a pyramid, a diamond, sphere, hemisphere, or a rectangularprism. In some embodiments, the diode is in the shape of a pyramid. Insome embodiments, the diode is in the shape of a cylinder. In someembodiments, the diode is manufactured using a conductive powder that issubjected to a patterning process. In some embodiments, the diode ismanufactured using a conductive or semi-conductive material that issubjected to a patterning process selected from: stamping, extrusion,printing, lithography, rolling, or combinations thereof. In someembodiments, the diode is manufactured using a conductive orsemi-conductive material that is subjected to a patterning processfollowed by heating. In some embodiments, the diode is manufacturedusing a conductive or semi-conductive material that is subjected to apatterning process followed by sintering, pyrolysis, or baking. In someembodiments, the diode is manufactured using a conductive polymer thatis subjected to a patterning process followed by pyrolysis. In someembodiments, the diode is manufactured using a conductive powder that issubjected to a patterning process followed by sintering. In someembodiments, at least some of the diodes have a porous surface. In someembodiments, at least some of the diodes have a non-porous surface.

Disclosed herein, in certain embodiments, is a photovoltaic cellcomprising: a plurality of three-dimensional electrodes comprising aconductive or semi-conductive material, wherein the conductive orsemi-conductive material is selected from: a metal, a metal alloy, anintermetallic material, a metallic glass, a composite material, apolymer, biocompatible material, or combinations thereof; and at leastone photoactive material; wherein the shape of the electrodes variesalong the vertical axis.

Disclosed herein, in certain embodiments, is a A three dimensionalelectrode comprising a conductive or semi-conductive material, whereinthe conductive or semi-conductive material is selected from: a metal, ametal alloy, an intermetallic material, a metallic glass, a compositematerial, a polymer, biocompatible material, or combinations thereof;and wherein the shape of the electrode varies along the vertical axis.

Disclosed herein, in certain embodiments, is an electroluminescent cellcomprising: a plurality of three-dimensional diodes comprising aconductive or semi-conductive material, wherein the conductive orsemi-conductive material is selected from: a metal, a metal alloy, anintermetallic material, a metallic glass, a composite material, apolymer, biocompatible material, or combinations thereof; and a currentsource; wherein the shape of the diodes varies along the vertical axis.

Disclosed herein, in certain embodiments, is a three dimensional diodecomprising a conductive or semi-conductive material, wherein theconductive or semi-conductive material is selected from: a metal, ametal alloy, an intermetallic material, a metallic glass, a compositematerial, a polymer, biocompatible material, or combinations thereof,and wherein the shape of the diode varies along the vertical axis.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention will be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 shows an array of 3 dimensionally fabricated micro electrodes.

FIG. 2 shows the 3-D architecture of an organic PV cell with the 3Delectrodes.

FIG. 3 shows the manufacturing steps for an electrode disclosed herein.The micro (or nano) stamping process is followed by a sintering process(here by a electric current).

FIG. 4 is a schematic representation of an array of 3D carbon electrodesarchitecture with separated trace pattern.

FIG. 5 is a schematic structure of the electron harvesting using the 3Delectrodes and polymeric photovoltaic interaction.

FIG. 6 shows the 3-D architecture with multiple photoactive layers ofdifferent types to absorb different peaks of spectrums within visiblelight.

FIG. 7 shows the 3-D electrode architecture with increased OLED surfaceareas.

FIG. 8 shows the 3-D architecture with a novel white tandem OLEDs byvertically stacking in series multiple electroluminescent layers.

FIG. 9 shows a 2-D cross-sectional view of the architecture of‘all-polymer’ Organic-MEMS/NEMS based organic photovoltaic cell. ‘d’ isthe depth of the cell and varies from 5 m to 25 m. Electrons arecollected through out the depth of the graphite cathode whereas holestravel to PEDOT:PSS layer that runs through the depth of the anodes. Thecircuit is completed through graphite wire traces which act as electronand hole conduction paths.

FIG. 10 shows the Fermi energy level diagrams and light harvestingrelative to vacuum level for the AllPoly system in flat band conditions.During light energy exposure, an electron is promoted to the LUMO(lowest unoccupied molecular orbital) leaving a hole behind in the HOMO(highest occupied molecular orbital). Electrons are collected in thepyrolysed carbon (graphite) electrode and holes at the PEDOT:PSSelectrode.

FIG. 11( a) shows the geometry of the chip that forms the basis of a 3-Dgraphite micro-electrode based photovoltaic cell. The electrodes have150 μm diameter with 350 μm spacing and traces of 75 μm width and bumppad of 1 mm×1 mm size. FIG. 11( b) is an SEM image after patterning.FIG. 11( c) is an SEM image of 3-D electrodes.

FIG. 12( a) shows a completed all-polymer photovoltaic cell with a 10×10array of 3-D graphite electrodes. FIG. 12( b) is an SEM image of asample anode after PEDOT:PSS was applied.

FIG. 13 shows images of 3-D graphite electrodes with photoactivematerials. FIG. 13( a) shows that heat treatment is found to offer asmoother topology. FIG. 13( b) shows that air-dried photoactivematerials tend to crystallize.

FIG. 14 shows the current reading for 5 A+5 C, 10 A+10 C, and 50 A+50 C(1-3 layers).

FIG. 15 shows the current reading for 50 A+50 C (3 layers) showingeffect of heat treatment.

FIG. 16 shows the current reading for 50 A+50 C, 10 A+10 C, and 5 A+5 C(all 1 layer) showing effect of number of electrodes.

FIG. 17 shows the variation of current with number of electrodes.

FIG. 18 shows the current reading for 50 A+50 C showing effect ofphotoactive material layers.

FIG. 19 shows Different configurations for optimizing exposed areas in3-D architecture of all-polymer solar cell.

FIG. 20 shows the variation of generated current with the vertical tiltof a chip. The chips are held at 45° in the horizontal plane.

FIG. 21 shows the variation of generated current with spacing ofelectrodes.

FIG. 22 shows the variation of incident light on an array of 5×5 3-Delectrodes as a function of horizontal angle of incidence of lightsource.

FIG. 23( a) shows a sintering setup for stationary and moving tipconfigurations. FIG. 23( b) is an SEM image of part of sintered nickellayer beneath the surface (˜50 μm thick) for moving tip configuration(C).

FIG. 24( a) shows the effect of number of cycles on the microhardness oflocally sintered (material surface immediately beneath the tip) nickelunder configuration A. It is clear that the hardness increases from ˜38HV for the green compact to over 200 HV after 70 current cycles, for ahighly sintered localized region. The increase in hardness becomessignificant after 30 cycles. FIG. 24( b) shows the grain growth that wasalso observed as the sintering proceeds.

FIG. 25( a) is an SEM micrograph of cross-section of sintered regionbeneath tip using configuration B. FIG. 25( b) is a hardness map of thecorresponding cross-section.

FIG. 26( a) is an SEM Micrograph of sintered subsurface along the tippath using configuration C. FIG. 26( b) shows a green compact withlocally sintered square impressions using configuration C.

FIG. 27 shows the details of four tested chips. FIG. 27( a) shows thedetails of a chip with four wires each connected to four sets of fiveelectrodes; two sets of five electrodes that serve as anodes werecovered with PEDOT:PSS; and the chip had seven layers. FIG. 27( b) showsthe details of a chip with five layers; the chip had a row of fiveelectrodes that were connected to form cathodes and another row of fiveelectrodes that were connected to form anodes; the cell comprised twowires connecting cathodes and anodes; and the electrodes were diamondshaped and heat treated. FIG. 27( c) shows the details of a chip thathad three layers; the chip had ten rows of five electrodes (i.e., 50electrodes) that were connected to form anodes, cathodes were formed ina similar fashion, the electrodes were diamond shaped and heat treated.FIG. 27( d) shows the details of a chip that had ten rows of fiveelectrodes (i.e., 50 electrodes) that were connected to form anodes,cathodes were formed in a similar fashion; the he electrodes werediamond shaped and were not heat treated.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein, in certain instances, is a novel photovoltaic cellthat uses unique micro-architectural and multi-layer functional designs.Currently, off-the-shelf silicon-based solar cell modules deliver energyefficiencies in the range of 15% with costs 30 cents to 40 cents per kWh(−10 cents/kWh for grid-connected US electricity). These novel cellswill offer an economic scale well below a target cost of about$4000/kWp, namely, under 20 cents/kWh if mass-produced, which is about50% of the cost of the state-of-the-art silicon-based photovoltaic cellsin current market.

Further disclosed herein, in certain instances, is a 3-dimensionalelectrode. As compared to traditional planar electrodes, thethree-dimensional electrode design disclosed herein increases thesurface contact areas (by 3 to 6 times) for thick photoactive layerswithout increasing the electrical resistance, and thus improving theenergy conversion efficiency.

Disclosed herein, in certain instances, is a novel electroluminescentcell that uses unique micro-architectural and multi-layer functionaldesigns.

Further disclosed herein, in certain instances, is a 3-dimensionaldiode. As compared to traditional planar diodes, the three-dimensionalelectrode design disclosed herein increases surface area.

I. Electrodes

Disclosed herein, in certain embodiments, is a three dimensionalelectrode comprising a conductive or semi-conductive material, whereinthe conductive or semi-conductive material is selected from: carbon, acarbon allotrope, or an organic polymer, and wherein the shape of theelectrode varies along the vertical axis. In some embodiments, theelectrode is an all-polymer electrode.

In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 5%, 10%, 15%, 20%, 25%, 30%, 40%, or 50%. In someembodiments, the photovoltaic cell provides energy conversion efficiencyof at least 5%. In some embodiments, the photovoltaic cell providesenergy conversion efficiency of at least 7%. In some embodiments, thephotovoltaic cell provides energy conversion efficiency of at least 10%.In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 15%. In some embodiments, the photovoltaic cellprovides energy conversion efficiency of at least 20%. In someembodiments, the photovoltaic cell provides energy conversion efficiencyof at least 25%. In some embodiments, the photovoltaic cell providesenergy conversion efficiency of at least 30%. In some embodiments, thephotovoltaic cell provides energy conversion efficiency of at least 40%.In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 50%.

In some embodiments, the electrode is an anode or a cathode. In someembodiments, the anode has a work function of 5 eV or higher. In someembodiments, the cathode has a work function of less than 5 eV.

Shape

In some embodiments, the electrode is a three-dimensional electrode. Insome embodiments, the three-dimensional electrodes are in the shape of acylinder, a pyramid, a diamond, sphere, hemisphere, or a rectangularprism. In some embodiments, the three-dimensional electrodes are in theshape of pyramids. In some embodiments, the three-dimensional electrodesare in the shape of cylinders. In some embodiments, utilizing athree-dimensional electrode increases the electrode/polymer contactsurface area and hence interaction. In some embodiments, the narrow gapbetween the three-dimensional electrodes enables fully operationaldevices with thick photoactive layers without increasing the resistance.In some embodiments, increasing the electrode/polymer contact surfacearea increases efficiency.

Manufacturing

In some embodiments, the electrode is manufactured using a patterningprocess, followed by heating. In some embodiments, the heating iscarried out by sintering, pyrolysis, or baking.

In some embodiments, the electrodes are manufactured by first patterninga conductive powder or polymer. In some embodiments, the patterningconsists of two layers. In some embodiments, the bottom layer is for thewire traces that connect a series of anodes and cathodes separately. Insome embodiments, the second layer consists of the high-aspect ratioelectrodes.

In some embodiments, the patterned polymer or powder is subjected toheating (e.g., sintering, pyrolysis, or baking). As used herein,“sintering” means heating a powder below its melting point until thepowder particles adhere to each other. As used herein, “pyrolysis” meanschemical decomposition of a condensed substance by heating.

In some embodiments, the conductive or semi-conductive material is apowder. In some embodiments, the polymer is a powder and the heating iscarried out by sintering. In some embodiments, sintering results in thepowder particles adhering to one another to form a single object. Insome embodiments, the sintering comprises the application of heat andpressure to a patterned powder. In some embodiments, the sinteringcomprises Joule heating and pressure to a patterned powder. In someembodiments, sequential layers of powders are deposited in-situfollowing each sintering path.

In some embodiments, the sintering is spark-plasma sintering (SPS). Insome embodiments, the SPS is administered through a tip. In someembodiments, the tip is at least 1 nm. In some embodiments, the tip isgreater than 1 nm. In some embodiments, when there is a small contactarea between the tip and the powder bed, the electric currentrequirement is low. In some embodiments, SPS enables the sintering ofnano-powders (and the retention of the nanostructure), micro-powders(and the retention of the microstructure), or macro-powders at lowtemperatures, in a short amount of time while using much higher heatingrates than conventionally possible. In some embodiments, SPS enablesshape and size of the electrode to be controlled by controlling the tipsize, position, path and speed.

The effect of an electric field on the diffusion flux (J_(i)) inaccordance with electromigration theory is detailed in the followingequation:

$J_{i} = {- {\frac{D_{i}C_{i}}{RT}\left\lbrack {\frac{{RT}{\partial\ln}\; C_{i}}{\partial x} + {{Fz}^{*}E}} \right\rbrack}}$where D_(i) is the diffusion coefficient, C_(i) is concentration, F isFaraday's Constant, z* is the effective charge on diffusing species, Tis the temperature, E is the field and R is the gas constant.

In some embodiments, the conductive or semi-conductive material is apolymer. In some embodiments, the heating is carried out by pyrolysis.In some embodiments, pyrolysis occurs under pressure, with no or minimaloxygen (e.g., less than stoichiometric quantities of oxygen), and atoperating temperatures above 430° C. In some embodiments, organicmaterials are transformed into gases, small quantities of liquid, and asolid residue (coke) containing fixed carbon and ash. In someembodiments, pyrolysis occurs in any suitable device (e.g., a rotarykiln, rotary hearth furnace, or fluidized bed furnace).

In some embodiments, once the 3-dimensional electrode is manufactured, aconductive polymer (e.g.,poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) or PEDOT:PSS)must be deposited on the surface of the electrode (e.g., for themanufacture of anodes). In some embodiments, the electrode ismanufactured on a wafer, metal or non-metal substrate, sheet or film. Insome embodiments, a lithographic technique is used to deposit a thicklayer of conductive polymer throughout the wafer, metal or non-metalsubstrate, sheet or film followed by photolithography to remove allconductive polymer from all regions except in the vicinity (1-2 micron)of the desired electrode.

In some embodiments, depositing a conductive polymer on an electroderequires scoring the electrode surface. In some embodiments, dry gasetching is used to create rough surfaces on the carbon electrodes. Insome embodiments, the photoactive-polymer is the spin-coated on theelectrode. In some embodiments, the conductive polymer is PEDOT:PSS. Insome embodiments, the anode has a work function of 5 eV or higher.

In some embodiments, the electrode has a porous surface. In someembodiments, porosity increases surface area. In some embodiments, theelectrode has a non-porous surface.

Materials

In some embodiments, the electrodes comprise a conductive orsemi-conductive material. In some embodiments, the electrodes comprise aconductive or semi-conductive material selected from: carbon, a carbonallotrope, or an organic polymer. In some embodiments, the electrodescomprise a conductive or semi-conductive material selected fromgraphite, diamond, amorphous carbon, buckminsterfullerenes, glassycarbon, carbon nanofoam, lonsdaleite, linear acetylenic carbon, orcombinations thereof. In some embodiments, the electrodes comprisegraphite. In some embodiments, the electrodes comprise glassy carbon. Asopposed to conventional metal electrodes, such as aluminum and indiumtin oxide, carbon-based electrodes are cheaper to manufacture. Carbon isabundantly availability—it is the fourth most abundant element on earth.Indium tin oxide is very scarce with world-wide supply projected to lastonly 10 years. Further, an expensive process is required to obtain agood quality ITO. Additionally, carbon has excellent electrochemicalstability, and good thermal and electrical conductivities.

In some embodiments, the electrodes comprise a conductive orsemi-conductive material selected from: a metal, a metal alloy, anintermetallic material, a metallic glass, a composite material, apolymer, biocompatible material, or combinations thereof. In someembodiments, the electrodes comprise SU-8 negative photoresist. In someembodiments, the electrodes comprise a metal. In some embodiments, theelectrodes comprise a metal alloy. In some embodiments, the electrodescomprise an intermetallic. In some embodiments, the electrodes comprisea metallic glass. In some embodiments, the electrodes comprise acomposite material. In some embodiments, the electrodes comprise abiocompatible material. In some embodiments, the electrodes comprise asemiconductor, a superconductor, or a combination thereof.

Methods of Manufacturing

Disclosed herein, in certain embodiments, is a method of manufacturing athree-dimensional electrode comprising: patterning a conductive orsemi-conductive material into the desired three-dimensional shape; andheating the patterned conductive or semi-conductive material. In someembodiments, the electrode is made from a polymer precursor. In someembodiments, the electrode is a made from a powder precursor that isconsolidated or partially consolidated. In some embodiments, theelectrode is made from carbon or a carbon allotrope.

In some embodiments, the electrode is manufactured using a patterningprocess, followed by heating. In some embodiments, the heating iscarried out to sinter, pyrolyze, or bake the precusor.

In some embodiments, the patterning process is any polymer 3D shapingprocess. In some embodiments, the patterning process is any powder 3Dshaping process. In some embodiments, the patterning process isstamping, extrusion, printing, lithography, rolling, or combinationsthereof. In some embodiments, the patterning process is ink-jetprinting. In some embodiments, the patterning process is stamping. Insome embodiments, the patterning process is roll-to-roll. In someembodiments, the patterning process is photolithography.

In some embodiments, the electrodes are manufactured by first patterninga conductive powder or polymer. In some embodiments, the patterningconsists of two layers. In some embodiments, the bottom layer is for thewire traces that connect a series of anodes and cathodes separately. Insome embodiments, the second layer consists of the high-aspect ratioelectrodes.

In some embodiments, the patterned polymer or powder is subjected toheating in order to sinter or pyroloyse and bake the feature. As usedherein, “sintering” means heating a powder below its melting point orabove the melting point of one or more of its constituents until thepowder particles adhere to each other. As used herein, “pyrolysis” meanschemical decomposition of a condensed substance by heating.

In some embodiments, the conductive or semi-conductive material is apowder. In some embodiments, the polymer is a powder and the heating iscarried-out to sinter the precursor. In some embodiments, sinteringresults in the powder particles adhering to one another to form a singleobject. In some embodiments, the sintering comprises the application ofheat (via conventional heat or current/field assisted heating) andpressure to a patterned powder. In some embodiments, the sinteringcomprises Joule heating and pressure to a patterned powder. In someembodiments, the sequential layers of powders are deposited in-situfollowing each sintering path.

In some embodiments, the sintering is spark-plasma sintering (SPS). Insome embodiments, the SPS is administered through a tip. In someembodiments, the tip is at least 1 nm. In some embodiments, the tip isgreater than 1 nm. In some embodiments, when there is a small contactarea between the tip and the powder bed, the electric currentrequirement is low. In some embodiments, SPS enables the sintering ofnano-powders (and the retention of the nanostructure), micro-powders(and the retention of the microstructure), or macro-powders at lowtemperatures, in a short amount of time while using much higher heatingrates than conventionally possible. In some embodiments, SPS enablesshape and size of the electrode to be controlled by controlling the tipsize, position, pat, speed, and environment.

In some embodiments, the sintering is conducted in a conventionalfurnace.

In some embodiments, the sintering of all or part of the patternedfeatures is conducted as a whole by passing electric current to thelayered structure

In some embodiments, the tip can be used for a dual function, whichincludes a pyrolysis stage of polymer or powder polymer followed by asintering stage of the pyrolysed polymer or powder for efficientconsolidation of controlled density.

The effect of an electric field on the diffusion flux (J_(i)) inaccordance with electromigration theory is detailed in the followingequation:

$J_{i} = {- {\frac{D_{i}C_{i}}{RT}\left\lbrack {\frac{{RT}{\partial\ln}\; C_{i}}{\partial x} + {{Fz}^{*}E}} \right\rbrack}}$where D_(i) is the diffusion coefficient, C_(i) is concentration, F isFaraday's Constant, z* is the effective charge on diffusing species, Tis the temperature, E is the field and R is the gas constant.

In some embodiments, the conductive or semi-conductive material is apolymer. In some embodiments, the heating is applied to pyrolyze theprecursor. In some embodiments, pyrolysis occurs under pressure, with noor minimal oxygen (e.g., less than stoichiometric quantities of oxygen),and at operating temperatures above 400° C. In some embodiments, organicmaterials are transformed into gases, small quantities of liquid, and asolid residue (coke) containing fixed carbon and ash. In someembodiments, pyrolysis occurs in any suitable device (e.g., a rotarykiln, rotary hearth furnace, or fluidized bed furnace).

In some embodiments, once the 3-dimensional electrode is manufactured, aconductive polymer (e.g.,poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) or PEDOT:PSS)must be deposited on the surface of the electrode (e.g., for themanufacture of anodes). In some embodiments, the electrode ismanufactured on a wafer, metal or non-metal substrate, sheet or film. Insome embodiments, a lithographic technique is used to deposit a thicklayer of conductive polymer throughout the wafer, metal or non-metalsubstrate, sheet or film followed by photolithography to remove allconductive polymer from all regions except in the vicinity (1-2 micron)of the desired electrode.

In some embodiments, depositing a conductive polymer on an electroderequires scoring the electrode surface. In some embodiments, dry gasetching is used to create rough surfaces on the carbon electrodes. Insome embodiments, the photoactive-polymer is the spin-coated on theelectrode. In some embodiments, the conductive polymer is PEDOT:PSS. Insome embodiments, the anode has a work function of 5 eV or higher.

Photovoltaic Cells

Current photovoltaic cells typically consist of a thin photoactive layer(e.g., about 100 nanometers) that is sandwiched between two metalelectrodes. In certain instances, the anode is a transparent, conductivemetal oxide (e.g., Indium Tin Oxide). In certain instances, the cathodeis aluminum.

The current architecture of photovoltaic cells (i.e., planar cells) issuch that the electron transfer length is limited to an extremely smallregion (e.g., about 10 to about 20 nanometers). As a result,photoelectric conversion in organic photovoltaic cells is often limitedto these small regions around the interfaces between donors andacceptors of the polymer photoactive blend. Such thin layers havelimited absorption even at the peak of their absorption spectrum sincethe optical absorption length is in the order of a few hundreds ofnanometers.

Disclosed herein, in certain embodiments, is a photovoltaic cellcomprising: (a) a plurality of three-dimensional electrodes comprising aconductive or semi-conductive material; and (b) at least one photoactivematerial; wherein the shape of the electrodes varies along the verticalor horizontal axis.

In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 5%, 10%, 15%, 20%, 25%, 30%, 40% or 50%. In someembodiments, the photovoltaic cell provides energy conversion efficiencyof at least 5%. In some embodiments, the photovoltaic cell providesenergy conversion efficiency of at least 7%. In some embodiments, thephotovoltaic cell provides energy conversion efficiency of at least 10%.In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 15%. In some embodiments, the photovoltaic cellprovides energy conversion efficiency of at least 20%. In someembodiments, the photovoltaic cell provides energy conversion efficiencyof at least 25%. In some embodiments, the photovoltaic cell providesenergy conversion efficiency of at least 30%. In some embodiments, thephotovoltaic cell provides energy conversion efficiency of at least 40%.In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 50%.

In some embodiments, the electrode is an all-polymer electrode. In someembodiments, the electrodes comprise carbon, a carbon allotrope, or anorganic polymer. In some embodiments, the electrodes comprise graphiteor glassy carbon. In some embodiments, electromagnetic radiation entersthe cell from at least two sides and contacts the photoactive material.In some embodiments, a photovoltaic cell disclosed herein has decreaseddiffusion length and increased light absorption area.

In some embodiments, the electromagnetic radiation is visible light(i.e., EM having a wavelength from about 380 to about 750 nm). In someembodiments, the electromagnetic radiation is infrared radiation (i.e.,EM radiation having a wavelength from about 700 nm to about 1 mm). Insome embodiments, the electromagnetic radiation is ultraviolet radiation(i.e., EM radiation having a wavelength from about 10 nm to about 400nm).

In some embodiments, the electromagnetic radiation is absorbed by thephotoactive material. In some embodiments, absorption of the photonsexcites electrons in a donor polymer, knocking them loose from theirorbit. In some embodiments, an electron hole is created when an electronis knocked loose from its orbit. In some embodiments, the hole flows tothe anode. In some embodiments, excited electrons migrate to thecathode. In some embodiments, the migration of holes to the anode andelectrons to the cathode creates a potential difference. In someembodiments, the diffusion length for migrating charges is less than 100nm.

Electrodes

In some embodiments, the electrodes are transparent and do not interferewith the ability of electromagnetic radiation to reach the photoactivematerials. Current photovoltaic cells utilize ITO-based anodes. Incertain instances, ITO-based anodes reduce the light energy transmissionenabling more electromagnetic radiation to reach the photoactivematerials. Further, current photovoltaic cells utilize aluminum-basedcathodes. In certain instances, the aluminum-based cathodes arenontransparent. Thus, in some embodiments, a photovoltaic cell disclosedherein allows the absorption of sun energy from multiple sides of thecell. This structure significantly increases the electrode/photoactivematerial interactions.

In some embodiments, the first electrode is an anode and the secondelectrode is a cathode. In some embodiments, the anode has a workfunction of 5 eV or higher. In some embodiments, the anodes enable holetransport. In some embodiments, the cathode has a work function of lessthan 5 eV.

In some embodiments, the anode is coated with a thin layer of conductingpolymer. In some embodiments, the anode is coated with PEDOT:PSS.

In some embodiments, the three-dimensional electrodes are in the shapeof a cylinder, a pyramid, a diamond, sphere, hemisphere, or arectangular prism. In some embodiments, the three-dimensional electrodesare in the shape of pyramids. In some embodiments, the three-dimensionalelectrodes are in the shape of cylinders. In some embodiments, utilizinga three-dimensional electrode increases the electrode/polymer contactsurface area and hence interaction. In some embodiments, the narrow gapbetween the three-dimensional electrodes enables fully operationaldevices with thick photoactive layers without increasing the resistance.In some embodiments, increasing the electrode/polymer contact surfacearea increases efficiency.

In some embodiments, the electrodes are manufactured by first patterninga conductive powder or polymer. In some embodiments, the patterningconsists of two layers. In some embodiments, the bottom layer is for thewire traces that connect a series of anodes and cathodes separately. Insome embodiments, the second layer consists of the high-aspect ratioelectrodes. In some embodiments, patterning occurs via photolithography.

In some embodiments, the electrode is manufactured using a patterningprocess, followed by heating. In some embodiments, the heating iscarried out to sinter, pyrolyze, or bake the precusor.

In some embodiments, the patterning process is any polymer 3D shapingprocess. In some embodiments, the patterning process is any powder 3Dshaping process. In some embodiments, the patterning process isstamping, extrusion, printing, lithography, rolling, or combinationsthereof. In some embodiments, the patterning process is ink-jetprinting. In some embodiments, the patterning process is stamping. Insome embodiments, the patterning process is roll-to-roll. In someembodiments, the patterning process is photolithography.

In some embodiments, the patterned polymer or powder is subjected toheating in order to sinter or pyroloyse and bake the feature. As usedherein, “sintering” means heating a powder below its melting point orabove the melting point of one or more of its constituents until thepowder particles adhere to each other. As used herein, “pyrolysis” meanschemical decomposition of a condensed substance by heating.

In some embodiments, the conductive or semi-conductive material is apowder. In some embodiments, the polymer is a powder and the heating iscarried-out to sinter the precursor. In some embodiments, sinteringresults in the powder particles adhering to one another to form a singleobject. In some embodiments, the sintering comprises the application ofheat (via conventional heat or current/field assisted heating) andpressure to a patterned powder. In some embodiments, the sinteringcomprises Joule heating and pressure to a patterned powder. In someembodiments, the sequential layers of powders are deposited in-situfollowing each sintering path.

In some embodiments, the sintering is spark-plasma sintering (SPS). Insome embodiments, the SPS is administered through a tip. In someembodiments, the tip is at least 1 nm. In some embodiments, the tip isgreater than 1 nm. In some embodiments, when there is a small contactarea between the tip and the powder bed, the electric currentrequirement is low. In some embodiments, SPS enables the sintering ofnano-powders (and the retention of the nanostructure), micro-powders(and the retention of the microstructure), or macro-powders at lowtemperatures, in a short amount of time while using much higher heatingrates than conventionally possible. In some embodiments, SPS enablesshape and size of the electrode to be controlled by controlling the tipsize, position, pat, speed, and environment.

In some embodiments, the sintering is conducted in a conventionalfurnace.

In some embodiments, the sintering of all or part of the patternedfeatures is conducted as a whole by passing electric current to thelayered structure

In some embodiments, the tip can be used for a dual function, whichincludes a pyrolysis stage of polymer or powder polymer followed by asintering stage of the pyrolysed polymer or powder for efficientconsolidation of controlled density.

The effect of an electric field on the diffusion flux (J_(i)) inaccordance with electromigration theory is detailed in the followingequation:

$J_{i} = {- {\frac{D_{i}C_{i}}{RT}\left\lbrack {\frac{{RT}{\partial\ln}\; C_{i}}{\partial x} + {{Fz}^{*}E}} \right\rbrack}}$where D_(i) is the diffusion coefficient, C_(i) is concentration, F isFaraday's Constant, z* is the effective charge on diffusing species, Tis the temperature, E is the field and R is the gas constant.

In some embodiments, the conductive or semi-conductive material is apolymer. In some embodiments, the heating is applied to pyrolyze theprecursor. In some embodiments, pyrolysis occurs under pressure, with noor minimal oxygen (e.g., less than stoichiometric quantities of oxygen),and at operating temperatures above 400° C. In some embodiments, organicmaterials are transformed into gases, small quantities of liquid, and asolid residue (coke) containing fixed carbon and ash. In someembodiments, pyrolysis occurs in any suitable device (e.g., a rotarykiln, rotary hearth furnace, or fluidized bed furnace).

In some embodiments, once the 3-dimensional electrode is manufactured, aconductive polymer (e.g.,poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) or PEDOT:PSS)must be deposited on the surface of the electrode (e.g., for themanufacture of anodes). In some embodiments, the electrode ismanufactured on a wafer, metal or non-metal substrate, sheet or film. Insome embodiments, a lithographic technique is used to deposit a thicklayer of conductive polymer throughout the wafer, metal or non-metalsubstrate, sheet or film followed by photolithography to remove allconductive polymer from all regions except in the vicinity (1-2 micron)of the desired electrode.

In some embodiments, depositing a conductive polymer on an electroderequires scoring the electrode surface. In some embodiments, dry gasetching is used to create rough surfaces on the carbon electrodes. Insome embodiments, the photoactive-polymer is the spin-coated on theelectrode. In some embodiments, the conductive polymer is PEDOT:PSS. Insome embodiments, the anode has a work function of 5 eV or higher.

In some embodiments, the electrode is porous. In some embodiments,porosity increases surface areas of the electrode

In some embodiments, the electrodes comprise a conductive orsemi-conductive or semi-conductive material. In some embodiments, theelectrodes comprise a conductive or semi-conductive or semi-conductivematerial selected from: carbon, a carbon allotrope, or an organicpolymer. In some embodiments, the electrodes comprise a conductive orsemi-conductive or semi-conductive material selected from graphite,diamond, amorphous carbon, buckminsterfullerenes, glassy carbon, carbonnanofoam, lonsdaleite, linear acetylenic carbon, or combinationsthereof. In some embodiments, the electrodes comprise graphite. In someembodiments, the electrodes comprise glassy carbon. As opposed toconventional metal electrodes, such as aluminum and indium tin oxide,carbon-based electrodes are cheaper to manufacture. Carbon is abundantlyavailability—it is the fourth most abundant element on earth. Indium tinoxide is very scarce with world-wide supply projected to last only 10years. Further, an expensive process is required to obtain a goodquality ITO. Additionally, carbon has excellent electrochemicalstability, and good thermal and electrical conductivities.

In some embodiments, the electrodes comprise a conductive orsemi-conductive or semi-conductive material selected from: a metal, ametal alloy, an intermetallic material, a metallic glass, a compositematerial, a polymer, biocompatible material, or combinations thereof. Insome embodiments, the electrodes comprise SU-8 negative photoresist.

In some embodiments, the electrodes comprise a metal. In someembodiments, the electrodes comprise a metal alloy. In some embodiments,the electrodes comprise an intermetallic. In some embodiments, theelectrodes comprise a metallic glass. In some embodiments, theelectrodes comprise a composite material. In some embodiments, theelectrodes comprise a biocompatible material. In some embodiments, theelectrodes comprise a semiconductor, a superconductor, or a combinationthereof.

In some embodiments, the sizes of individual 3D electrodes are from afew nanometers to several mm. In some embodiments, the spacing betweenelectrodes is from a few nanometers to several mm.

Photoactive Material

In some embodiments, the photoactive material surrounds the firstelectrode and the second electrode.

In some embodiments, the first photoactive material comprises a matrixof heterojunction photoactive material. In some embodiments, the firstphotoactive material comprises crystalline silicone, cadmium telluride,copper-indium selenide, copper indium/gallium diselenide, rutheniummetalorganic dye, P3HT (poly(3-hexylthiophene)), PCBM(phenyl-C61-butyric acid methyl ester), or combinations thereof. In someembodiments, the photoactive material comprises P3HT(poly(3-hexylthiophene)) and PCBM (phenyl-C61-butyric acid methylester). In some embodiments, the photoactive material comprises P3HT(poly(3-hexylthiophene)) and PCBM (phenyl-C61-butyric acid methyl ester)in a 1:1 ratio by weight.

In some embodiments, the 3D architecture of the cell supports multiplephotoactive layers. In some embodiments, the cell further comprises asecond photoactive material; and wherein the absorption spectrum of thefirst photoactive material and the absorption of the second photoactivematerial are different. In some embodiments, the use of multiplephotoactive layers enables increased absorption of photonic energy andhence increased efficiency. In certain instances, visible light tends tohave an average of 51% of photon energy whereas infrared (IR) could haveas much as 45% of photon energy. Thus, in some embodiments, theintroduction of a varying depth of photoactive region will enable theharvesting of more bandwidth in the spectrum.

In some embodiments, the surface area of the photoactive material isincreased by a factor of about 3 to about 6.

Patterns of the Electrodes on the Wafer, Metal or Non-Metal Substrate,Sheet or Film

In some embodiments, the first electrode and the second electrode arearranged in a plain structure.

In some embodiments, the first electrode and the second electrode arearranged in a grouped pattern.

In some embodiments, the first electrode and the second electrode arearranged in a separated pattern.

In some embodiments, the electrodes are formed in a no tracearchitecture. In some embodiments, the diodes is formed with a tracearchitecture. As used herein, “trace”, means the equivalent of a wirefor conducting signals. In some embodiments, a trace consists of a flat,narrow part of the copper foil that remains after etching.

In some embodiments, the cell has a single layer of photoactive materialand no trace pattern. In some embodiments, the cell has a single layerof photoactive material and a separated pattern. In some embodiments,the cell has a single layer of photoactive material and a groupedpattern.

In some embodiments, the cell has more than one layer of photoactivematerial and no trace pattern. In some embodiments, the cell has morethan one layer of photoactive material and a separated pattern. In someembodiments, the chip has more than one layer of photoactive materialand a grouped pattern.

Transparent Material

In some embodiments, the photovoltaic cell is surrounded by atransparent material, wherein the transparent material protects the cellfrom oxidation. In some embodiments, the photovoltaic cell is surroundedby a transparent material of glass, plastic, ceramic or a combinationthereof. In some embodiments, the photovoltaic cell is surrounded by atransparent material of glass, wherein the glass protects the cell fromoxidation. In some embodiments, the photovoltaic cell is surrounded by atransparent material of plastic, wherein the glass protects the cellfrom oxidation.

Uses

In some embodiments, the cell is used to make a solar module. As usedherein, a “solar module” means an interconnected assembly of solarcells.

II. Diodes

Disclosed herein, in certain embodiments, is a three dimensional diodecomprising a transparent conductive or semi-conductive orsemi-conductive material, wherein the shape of the diode varies alongthe vertical axis. In some embodiments, the diode is an all-polymerdiode.

In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 5%, 10%, 15%, 20%, 25%, 30%, 40% or 50%. In someembodiments, the photovoltaic cell provides energy conversion efficiencyof at least 5%. In some embodiments, the photovoltaic cell providesenergy conversion efficiency of at least 7%. In some embodiments, thephotovoltaic cell provides energy conversion efficiency of at least 10%.In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 15%. In some embodiments, the photovoltaic cellprovides energy conversion efficiency of at least 20%. In someembodiments, the photovoltaic cell provides energy conversion efficiencyof at least 25%. In some embodiments, the photovoltaic cell providesenergy conversion efficiency of at least 30%. In some embodiments, thephotovoltaic cell provides energy conversion efficiency of at least 40%.In some embodiments, the photovoltaic cell provides energy conversionefficiency of at least 50%.

In some embodiments, the diode comprises carbon, a carbon allotrope, oran organic polymer. In some embodiments, the diode comprises graphite orglassy carbon. In some embodiments, the diode comprises an anode and acathode.

Shape

In some embodiments, the diode is in the shape of a cylinder, a pyramid,a diamond, sphere, hemisphere, or a rectangular prism. In someembodiments, the diode is in the shape of a pyramid. In someembodiments, the three-dimensional electrodes are in the shape ofcylinders.

Manufacturing

In some embodiments, the diodes are manufactured by first patterning aconductive powder or polymer. In some embodiments, the patterningconsists of two layers. In some embodiments, the bottom layer is for thewire traces that connect a series of diode. In some embodiments, thesecond layer consists of the high-aspect ratio diodes.

In some embodiments, the patterning process is any polymer 3D shapingprocess. In some embodiments, the patterning process is any powder 3Dshaping process. In some embodiments, the patterning process isstamping, extrusion, printing, lithography, rolling, or combinationsthereof. In some embodiments, the patterning process is ink-jetprinting. In some embodiments, the patterning process is stamping. Insome embodiments, the patterning process is roll-to-roll. In someembodiments, the patterning process is photolithography.

In some embodiments, the patterned polymer or powder is subjected toheating (e.g., sintering, pyrolysis, or baking). As used herein,“sintering” means heating a powder below its melting point until thepowder particles adhere to each other. As used herein, “pyrolysis” meanschemical decomposition of a condensed substance by heating.

In some embodiments, the conductive or semi-conductive orsemi-conductive material is a powder. In some embodiments, the polymeris a powder and the heating is carried out by sintering. In someembodiments, sintering results in the powder particles adhering to oneanother to form a single object. In some embodiments, the sinteringcomprises the application of heat and pressure to a patterned powder. Insome embodiments, the sintering comprises Joule heating and pressure toa patterned powder. In some embodiments, the sequential layers ofpowders are deposited in-situ following each sintering path.

In some embodiments, the sintering is spark-plasma sintering (SPS). Insome embodiments, the SPS is administered through a tip. In someembodiments, the tip is about 1 nm. In some embodiments, the tip isgreater than 1 nm. In some embodiments, when there is a small contactarea between the tip and the powder bed, the electric currentrequirement is low. In some embodiments, SPS enables the sintering ofnano-powders (and the retention of the nanostructure), micro-powders(and the retention of the microstructure), or macro-powders at lowtemperatures, in a short amount of time while using much higher heatingrates than conventionally possible. In some embodiments, SPS enablesshape and size of the diode to be controlled by controlling the tipsize, position, path and speed.

The effect of an electric field on the diffusion flux (J_(i)) inaccordance with electromigration theory is detailed in the followingequation:

$J_{i} = {- {\frac{D_{i}C_{i}}{RT}\left\lbrack {\frac{{RT}{\partial\ln}\; C_{i}}{\partial x} + {{Fz}^{*}E}} \right\rbrack}}$where D_(i) is the diffusion coefficient, C_(i) is concentration, F isFaraday's Constant, z* is the effective charge on diffusing species, Tis the temperature, E is the field and R is the gas constant.

In some embodiments, the conductive or semi-conductive orsemi-conductive material is a polymer. In some embodiments, the heatingis carried out by pyrolysis. In some embodiments, pyrolysis occurs underpressure, with no or minimal oxygen (e.g., less than stoichiometricquantities of oxygen), and at operating temperatures above 430° C. Insome embodiments, organic materials are transformed into gases, smallquantities of liquid, and a solid residue (coke) containing fixed carbonand ash. In some embodiments, pyrolysis occurs in any suitable device(e.g., a rotary kiln, rotary hearth furnace, or fluidized bed furnace).

In some embodiments, once the 3-dimensional diode is manufactured, aconductive polymer (e.g.,poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) or PEDOT:PSS)must be deposited on part or all of the surface of the diode (e.g., forthe manufacture of the anode portion). In some embodiments, the diode ismanufactured on a wafer, metal or non-metal substrate, sheet or film. Insome embodiments, a lithographic technique is used to deposit a thicklayer of conductive polymer throughout the wafer, metal or non-metalsubstrate, sheet or film followed by photolithography to remove allconductive polymer from all regions except in the vicinity (1-2 micron)of the desired diode.

In some embodiments, depositing a conductive polymer on a diode requiresscoring the diode surface. In some embodiments, dry gas etching is usedto create rough surfaces on the carbon diodes. In some embodiments, thephotoactive-polymer is the spin-coated on the diode. In someembodiments, the conductive polymer is PEDOT:PSS. In some embodiments,the anode has a work function of 5 eV or higher.

In some embodiments, the diode is porous. In some embodiments, porosityincreases surface area.

Materials

In some embodiments, the diodes comprise a conductive or semi-conductiveor semi-conductive material. In some embodiments, the diodes comprise aconductive or semi-conductive material selected from: carbon, a carbonallotrope, or an organic polymer. In some embodiments, the diodescomprise a conductive or semi-conductive material selected fromgraphite, diamond, amorphous carbon, buckminsterfullerenes, glassycarbon, carbon nanofoam, lonsdaleite, linear acetylenic carbon, orcombinations thereof. In some embodiments, the diode comprises graphite.In some embodiments, the diode comprises glassy carbon. As opposed toconventional metal diodes, such as aluminum and indium tin oxide,carbon-based diodes are cheaper to manufacture. Carbon is abundantlyavailability—it is the fourth most abundant element on earth. Indium tinoxide is very scarce with world-wide supply projected to last only 10years. Further, an expensive process is required to obtain a goodquality ITO. Additionally, carbon has excellent electrochemicalstability, and good thermal and electrical conductivities.

In some embodiments, the diodes comprise a conductive or semi-conductivematerial selected from: a metal, a metal alloy, an intermetallicmaterial, a metallic glass, a composite material, a polymer,biocompatible material, or combinations thereof. In some embodiments,the diodes comprise SU-8 negative photoresist. In some embodiments, thediode comprises a metal. In some embodiments, the diode comprises ametal alloy. In some embodiments, the diode comprises an intermetallic.In some embodiments, the diode comprises a metallic glass. In someembodiments, the diode comprises a composite material. In someembodiments, the diode comprises a biocompatible material. In someembodiments, the diode comprises a semiconductor, a superconductor, or acombination thereof.

Conductive Polymer Coatings

In some embodiments, the anode is coated with a thin layer of conductingpolymer. In some embodiments, the anode is coated with PEDOT:PSS.

Methods of Manufacturing

Disclosed herein, in certain embodiments, is a method of manufacturing athree-dimensional diode comprising: patterning a conductive orsemi-conductive material into the desired three-dimensional shape; andheating the patterned conductive or semi-conductive material. In someembodiments, the diode is an all-polymer diode. In some embodiments, thediode comprises carbon, a carbon allotrope, or an organic polymer. Insome embodiments, the diode comprises graphite or glassy carbon.

In some embodiments, the patterning process is any polymer 3D shapingprocess. In some embodiments, the patterning process is any powder 3Dshaping process. In some embodiments, the patterning process isstamping, extrusion, printing, lithography, rolling, or combinationsthereof. In some embodiments, the patterning process is ink-jetprinting. In some embodiments, the patterning process is stamping. Insome embodiments, the patterning process is roll-to-roll. In someembodiments, the patterning process is photolithography.

In some embodiments, the heating is carried out by sintering, pyrolysis,or baking.

In some embodiments, the conductive or semi-conductive material is apowder. In some embodiments, the polymer is a powder and the heating iscarried out by sintering. In some embodiments, sintering results in theconsolidation of the powder into a single object. In some embodiments,the sintering comprises the application of heat and pressure. In someembodiments, the sintering comprises Joule heating and pressure. In someembodiments, the sintering is spark-plasma sintering. In someembodiments, sequential layers of powders are deposited in-situfollowing each sintering path.

In some embodiments, the sintering is administered through a tip. Insome embodiments, the tip is 1 nm. In some embodiments, the tip isgreater than 1 nm. In some embodiments, the sintering is controlled byvarying tip size, position, path and speed.

In some embodiments, the conductive or semi-conductive material is apolymer. In some embodiments, the heating is carried out by pyrolysis.In some embodiments, pyrolysis occurs under pressure, with no or minimaloxygen (e.g., less than stoichiometric quantities of oxygen), and atoperating temperatures above 430° C. In some embodiments, organicmaterials are transformed into gases, small quantities of liquid, and asolid residue (coke) containing fixed carbon and ash. In someembodiments, pyrolysis occurs in any suitable device (e.g., a rotarykiln, rotary hearth furnace, or fluidized bed furnace).

In some embodiments, the method further comprises scoring the diode. Insome embodiments, the diode is scored by dry gas etching. In someembodiments, the method further comprises depositing a photoactivepolymer on part of the diode. In some embodiments, the photoactivepolymer is PEDOT:PSS.

LED Cells

Disclosed herein, in certain embodiments, is an electroluminescent cellcomprising: (a) a plurality of three-dimensional diodes comprising aconductive or semi-conductive material; and (b) a current source;wherein the shape of the diodes varies along the vertical axis, andwherein the electroluminescent cell provides energy conversionefficiency of at least 10%. In some embodiments, the diode is anall-polymer electrode. In some embodiments, the diode comprises carbon,a carbon allotrope, or an organic polymer. In some embodiments, thediode comprises graphite or glassy carbon. In some embodiments, the cellis an organic LED. In some embodiments, the diode is transparent.

In some embodiments, the first polymer is the donor material. In someembodiments, the donor material emits electrons. In some embodiments,the second polymer is the acceptor material. In some embodiments, theacceptor material comprises holes. In some embodiments an electronrecombines with a hole. In some embodiments, the recombining of anelectron and a hole results in the electron falling into a lower energylevel. In some embodiments, the falling of the electron into a lowerenergy level releases a photon.

Diodes

In some embodiments, the diode comprises an anode and a cathode. In someembodiments, the anode is coated with a thin layer of conductingpolymer. In some embodiments, the anode is coated with PEDOT:PSS.

In some embodiments, the three-dimensional diode is in the shape of acylinder, a pyramid, a diamond, sphere, hemisphere, or a rectangularprism. In some embodiments, the three-dimensional diode is in the shapeof a pyramid. In some embodiments, the three-dimensional electrodes arein the shape of cylinders.

In some embodiments, the electrodes are manufactured by first patterninga conductive powder or polymer. In some embodiments, the patterningconsists of two layers. In some embodiments, the bottom layer is for thewire traces that connect a series of anodes and cathodes separately. Insome embodiments, the second layer consists of the high-aspect ratioelectrodes. In some embodiments, patterning occurs via photolithography.

In some embodiments, the patterning process is any polymer 3D shapingprocess. In some embodiments, the patterning process is any powder 3Dshaping process. In some embodiments, the patterning process isstamping, extrusion, printing, lithography, rolling, or combinationsthereof. In some embodiments, the patterning process is ink-jetprinting. In some embodiments, the patterning process is stamping. Insome embodiments, the patterning process is roll-to-roll. In someembodiments, the patterning process is photolithography.

In some embodiments, the patterned polymer or powder is subjected toheating (e.g., sintering, pyrolysis, or baking). As used herein,“sintering” means heating a powder below its melting point until thepowder particles adhere to each other. As used herein, “pyrolysis” meanschemical decomposition of a condensed substance by heating.

In some embodiments, the conductive or semi-conductive material is apowder. In some embodiments, the polymer is a powder and the heating iscarried out by sintering. In some embodiments, the sintering results inthe consolidation of the powder into a single object. In someembodiments, the sintering comprises the application of heat andpressure. In some embodiments, the sintering comprises Joule heating andpressure. In some embodiments, the sintering is spark-plasma sintering.In some embodiments, the sequential layers of powders are depositedin-situ following each sintering path.

In some embodiments, the sintering is administered through a tip. Insome embodiments, the tip is 1 nm. In some embodiments, the tip isgreater than 1 nm. In some embodiments, the sintering is controlled byvarying tip size, position, path and speed.

In some embodiments, the conductive or semi-conductive material is apolymer. In some embodiments, the heating is carried out by pyrolysis.In some embodiments, pyrolysis occurs under pressure, with no or minimaloxygen (e.g., less than stoichiometric quantities of oxygen), and atoperating temperatures above 430° C. In some embodiments, organicmaterials are transformed into gases, small quantities of liquid, and asolid residue (coke) containing fixed carbon and ash. In someembodiments, pyrolysis occurs in any suitable device (e.g., a rotarykiln, rotary hearth furnace, or fluidized bed furnace).

In some embodiments, the part or all of the diode is scored. In someembodiments, part or all of the diode is scored by dry gas etching. Insome embodiments, part or all of the diode further comprises aphotoactive polymer. In some embodiments, the photoactive polymer isPEDOT:PSS.

In some embodiments, the diodes comprise a conductive or semi-conductivematerial. In some embodiments, the diodes comprise a conductive orsemi-conductive material selected from: carbon, a carbon allotrope, oran organic polymer. In some embodiments, the diodes comprise aconductive or semi-conductive material selected from graphite, diamond,amorphous carbon, buckminsterfullerenes, glassy carbon, carbon nanofoam,lonsdaleite, linear acetylenic carbon, or combinations thereof. In someembodiments, the diode comprises graphite. In some embodiments, thediode comprises glassy carbon. As opposed to conventional metal diodes,such as aluminum and indium tin oxide, carbon-based diodes are cheaperto manufacture. Carbon is abundantly availability—it is the fourth mostabundant element on earth. Indium tin oxide is very scarce withworld-wide supply projected to last only 10 years. Further, an expensiveprocess is required to obtain a good quality ITO. Additionally, carbonhas excellent electrochemical stability, and good thermal and electricalconductivities.

In some embodiments, the diodes comprise a conductive or semi-conductivematerial selected from: a metal, a metal alloy, an intermetallicmaterial, a metallic glass, a composite material, a polymer,biocompatible material, or combinations thereof. In some embodiments,the diodes comprise SU-8 negative photoresist. In some embodiments, thediode comprises a metal. In some embodiments, the diode comprises ametal alloy. In some embodiments, the diode comprises an intermetallic.In some embodiments, the diode comprises a metallic glass. In someembodiments, the diode comprises a composite material. In someembodiments, the diode comprises a biocompatible material. In someembodiments, the diode comprises a semiconductor, a superconductor, or acombination thereof.

In some embodiments, the diode is porous. In some embodiments, porosityincreases surface area.

In some embodiments, the sizes of individual 3D diodes are from a fewnanometers to several mm. In some embodiments, the spacing betweendiodes is from a few nanometers to several mm.

Patterns of the Diodes on the Wafer, Metal or Non-Metal Substrate, Sheetor Film

In some embodiments, the cell comprises more than one diode.

In some embodiments, a first electrode and a second diode are arrangedin a plain structure.

In some embodiments, a first diode and a diode electrode are arranged ina grouped pattern.

In some embodiments, a first diode and a second diode are arranged in aseparated pattern.

In some embodiments, the electrodes are formed in a no tracearchitecture. In some embodiments, the diodes is formed with a tracearchitecture. As used herein, “trace”, means the equivalent of a wirefor conducting signals. In some embodiments, a trace consists of a flat,narrow part of the copper foil that remains after etching.

Transparent Material

In some embodiments, the electroluminescent cell is surrounded by atransparent material, wherein the transparent material protects the cellfrom oxidation. In some embodiments, the electroluminescent cell issurrounded by a transparent material of glass, plastic, ceramic or acombination thereof. In some embodiments, the electroluminescent cell issurrounded by a transparent material of glass, wherein the glassprotects the cell from oxidation. In some embodiments, theelectroluminescent cell is surrounded by a transparent material ofplastic, wherein the glass protects the cell from oxidation.

Uses

In some embodiments, the cell is used to make a flexible display, alight source, a wall decoration, or a light-emitting cloth.

EXAMPLES Example 1 Organic Photovoltaic Cell

Fabrication

C-MEMS (Organic MEMS) process was used for the microfabrication of 3-Delectrode microarray. Three-dimensional photoresist-derived carbonelectrodes with a height of 200 μm on top of a silicon substrate wereobtained by using conventional photolithography followed by pyrolysis.The electrodes have 150 μm diameter with 350 μm spacing and traces of 75μm width and bump pad of 1 mm×1 mm size. Due to shrinkage duringpyrolysis, photoresist layer for the electrode posts was spin-coatedwith a thickness of 220 μm initially to obtain final height of 200 μm.The overall chip size is 1 cm×1 cm.

Materials

PCBM was purchased from Nano-C (Westwood, Mass.) and used withoutfurther purification. P3HT was purchased from Rieks Metal Inc.,(Lincoln, Nebr.). PEDOT:PSS (poly-3,4-ethylenedioxy-thiophene) wasbought from Sigma-Aldrich (St. Louis, Mo.). The solvent dichlorobenzenewas bought from Sigma-Aldrich (St. Louis, Mo.).

Preparation of Materials

A blend of P3HT/PCBM was prepared by mixing P3HT and PCBM in 1:1 ratioby weight and dissolving the mixture in chlorobenzene. 0.0133 grams ofP3HT and PCBM each was dissolved in 1 mL of dichlorobenzene solution andwas incubated for 27 hours. The mix was shook for 3 hours inside theincubator. Additional 0.0133 grams of each was then added to the mix andthen shook for another 48 hours.

Dispensing of Materials

The substrate was cleaned in an ultrasonic bath of acetone (highperformance liquid chromatography (HPLC) grade) for 20 min, followed byisopropyl alcohol (IPA) (HPLC grade) rinsing for 20 minutes at roomtemperature, before being dried in a nitrogen gas flow. The cathodeswere masked by a photoresist. The PEDOT:PSS was applied throughspin-coating layer was then dried at 120° C. for 5 min.

The photoactive layer, consisting of a blend of P3HT and PCBM was thenapplied on the chip substrate using 40 micro liter pipette covering thePEDOT:PSS and pyrolysed carbon layer (for anodes) and just the pyrolysedcarbon layer for cathodes. This was done at room temperature under afume hood and there was no shaking or stirring. Half of the chips weredried under air through convection for 2.5 hours while the remaininghalf were dried on a hot plate heated to 65° C. for 20 minutes. Severallayers of photoactive material were deposited to reach the 200 μm depth.The thickness of each polymer blend layer was about 30 μm each resultingin seven layers.

Wire Bonding—This was done before the deposition of PEDOT:PSS and thepolymer blend. We used a wire bonder with the stage heated at 100° C.for 2 hours using 1:1 volume of two conducting epoxy resins. Afterdrying, conducting glue was applied and further dried for 15 minutes at100° C.

Testing and Measurements

A total of four types were made. Each chip was tested by putting thechips on a flat surface and expose to 1000 W/m2 with AM1.5 filter. Thewires were connected to a multi-meter. The chips were rotated both inthe horizontal and vertical planes to determine the most optimum currentgeneration conditions. In the horizontal plane, 45° was found to beoptimum whereas in the vertical plane, readings are taken every 10°until 45°.

The control chip had four wires each connected to four sets of fiveelectrodes. Two sets of five electrodes that serve as anodes werecovered with PEDOT:PSS. The chip had seven layers. The bottom six layershad good structure. The last layer showed globules which are suspectedto be crystals. See FIG. 27( a).

The spider chip had five layers. The chip had a row of five electrodesthat were connected to form cathodes and another row of five electrodesthat were connected to form anodes. Further, the cell comprised twowires connecting cathodes and anodes. The electrodes were diamond shapedand heat treated. See FIG. 27( b).

The heat treated 50 C+50 A cell had three layers. The chip had ten rowsof five electrodes (i.e. 50 electrodes) that were connected to formanodes. Cathodes were formed in a similar fashion. The electrodes werediamond shaped and heat treated. See FIG. 27( c).

The heat treated 50 C+50 A cell had three layers. The chip had ten rowsof five electrodes (i.e. 50 electrodes) that were connected to formanodes. Cathodes were formed in a similar fashion. The electrodes werediamond shaped and were not heat treated. See FIG. 27( d).

Example 2 Surface Morphology

The surface morphology of the different chips was investigated usingoptical microscopy after the application of photovoltaic blend andPEDOT:PSS layer. FIG. 12 shows one such result with optical microscopyimages of one of the chip sets (10×10 array) after five layers ofphotoactive blend are added.

5×5 and 10×10 arrays of 3-D electrodes with one, two, and five layers ofa photoactive polymer blend were generated. It was observed that heattreatment tends to offer a smoother topology whereas air-driedphotoactive materials tend to de-segregate into their constituent P3HTand PCBM.

Example 3 Photovoltaic Properties

The samples were subjected to light intensity of 1000 W/m2 with AM1.5filter and the current generated is measured by multi-meter.

We investigated the influence of a number of parameters on thephotovoltaic response of the new chip. These parameters are: depth andnumber of photoactive of layer, heat treatment, number of electrodeswired for charge collections (5/10/50 cathodes/anodes), effect ofPEDOT:PSS.

The results are summarized in FIGS. 13-20. FIG. 13 shows currentreadings for all tested chips. FIG. 14 shows that heat treatmentproduces more current carrying capacity. It is known that graphiteelectrodes have better conductivity when heated to moderate degree. Theeffect of number of electrodes is shown in FIGS. 15 and 16. It can beobserved that a fifty cathodes and fifty anodes configuration at 350micron spacing gives a maximum of 20 micro Amps of current. It can beinferred that a 1 cm×1 cm chip could have a total of 30×30 array at thesame spacing resulting in a 450 anode and 450 cathode configuration withcurrent generation of 200 micro Amps/cm2. The effect of spacing isinvestigated by building much denser arrays.

Next, the effect of electrode spacing and electrode density isinvestigated (see Table 1). The range of electrode spacing consideredvaries from 350 μm down to 50 μm. In subsequent generations of chips,tighter spacing going down to micron and sub-micron levels will beconsidered. The current densities corresponding to these ranges are 20mA/cm2 to 100 mA/cm2.

TABLE 1 Electrode Current Density Chip Size Array Size Spacing Current(A) (A/cm²) 1 cm × 1 cm 10 × 10 350 μm  20 mA 20 mA/cm² 30 × 30 350 μm 200 mA  200 mA/cm²  50 × 50 150 μm   2 mA  2 mA/cm² 75 × 75 75 μm 10 mA10 mA/cm² 100 × 100 50 μm 100 mA  100 mA/cm²  1 cm × 1 cm 200 × 200 20μm Generation II Generation II 250 × 250 10 μm ″ ″ 500 × 500  1 μm ″ ″750 × 750 0.5 μm  ″ ″ Polymer Ref — — — 10 mA/cm² [41]

Example 4 Sintering of Nanoscopic Nickel Powder

Nickel powder with 200-500 nm particle size (INCO 210H) was used in allexperiments. Three experimental/sample configurations were investigated.These are shown in table 2.

TABLE 2 Current Tip Green Compact Green Density Frequency Tip SpeedDiameter Dimensions (% of Configuration (Hz) (mm/s) (mm) (mm)theoretical) A 0.083 0.0 2.00 Diameter: 19.2 51 (2 s on: 10 s(Stationary) Thickness: 2.5 off) B 0.083 0.0 1.02 Diameter: 14.3 62 (2 son: 10 s (Stationary) Thickness: 2.7 off) C 60    16.7  0.021 Diameter:14.3 75 (AC) (Moving) Thickness: 3.0

Green compacts were placed on a conductive holder, and a tungsten(configuration A and B) or a copper (configuration C) tip was used toapply the contacting pressure and current.

For the moving tip configuration (C), the tip was connected to a CNCprogrammable XYZ stage that traced a square shape with a travel speed of16.7 mm/sec and an estimated contact force of ˜1 mN, and consequentlyresulted in a sintered square impression. For the stationary tip, directcurrent (giving a nominal current density of 1,833 A/cm² forconfiguration A and 12,732 A/cm² for configuration B) was used with a 2s on 10 s off duty cycle, while for the moving tip (configuration C), acontinuous AC current (60 Hz) was used with an estimated current densityof ˜1×107 A/cm2.

For both the stationary tip and the moving tip configurations, the inputvoltage was 2-5V. The setup is shown in FIG. 23. For microstructuralobservations, specimens were sectioned and polished to 1 μm finish.Microhardness was conducted using a 500 g load.

For configuration B, the microhardness of the sintered region (at adistance of 250 μm beneath the tip) as seen in FIG. 24( b), increasesabruptly with number of cycles. The hardness at 0 cycles is that for thegreen compact, which is higher than that of the green compact inconfiguration A due to its higher initial green density as seen in table4. The level of sintering and corresponding hardness is equivalent tothat of configuration A, after only 5 cycles. This is largerly due to asignificantly higher current density which was achieved by a reductionin the tip size compared to configuration A. The increase in currentdensity substantially increases the sintering rate. This is in line withclear observations of increased mass transport under the influence ofcurrent. It is anticipated that further reduction in tip size wouldresult in an even higher increase in sintering rate and a reduction insintering time. This is exemplified in the results of the moving tipconfiguration C below, which may have significant implications for rapidnano and microfabrication. Another observation is that the sintereddepth beneath the tip was also found to increase with number of cycles.

FIG. 25( a) is an SEM micrograph of the subsurface cross-section beneaththe tip of the locally sintered region (configuration B). It is clearthat shrinkage beneath the tip has occurred, while bulk shrinkageappears to have resulted in the formation of cracks. These cracksseparate the sintered region from the remaining green compact. It alsoshows a tunneling effect for the current, where locallized sintering isrealized. Microhardness mapping confirms the degree of sintering withinthe locallized region as compared to the surrounding green compact. Thiscan clearly be seen in FIG. 25( b), where points A and B possessapproximately the same hardness values while point E which is outsidethe locally sintered region still posesses the hardness value of thegreen compact. The hardness value of point D is lower than that of pointC, indicating a narrowing of the sintered region with depth beneath thesurface.

For the moving tip configuration (C), localized compactshrinkage/impression was observed beneath the copper tip following itspassage due to sintering (see FIG. 26( b)). This was not howeverobserved when the tip traced the same shape in the absence of current.Following CATS, the specimens were sectioned along/parallel to thesintered path, in order to observe/characterize the region beneath tip(see FIG. 26( a)). FIG. 26( a) shows that a region ˜50 μm beneath thetip was sintered compared to the remaining regions in the compact. Thelocalization and rapid sintering effect seen for configuration C islargely due to the excessively high current density (˜1×10⁷ A/cm²)promoting exceedingly rapid sintering rates and the high tip speed (16.7mm/s) which acts to confine conduction away from the tip thus promotinglocalization of the sintering to a small region below the tip. Someresidual porosity was also observed as seen in FIG. 26( a), however at adifferent level and scale compared to the remainder of the un-sinteredcompact. It must be mentioned that as shown in FIG. 26( b), sparking canoccur if the tip is removed prior to de-activating the current, whichleads to minor pit formation. Hence, maintaining contact between the tipand the powder surface during sintering appears to be important.

While preferred embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the invention. It should be understoodthat various alternatives to the embodiments of the invention describedherein may be employed in practicing the invention. It is intended thatthe following claims define the scope of the invention and that methodsand structures within the scope of these claims and their equivalents becovered thereby.

We claim:
 1. An electroluminescent cell comprising: a) a microarray ofthree-dimensional diodes comprising a conductive or semi-conductivematerial, each of said three-dimensional diodes shaped as a uniformlyspaced apart three-dimensional post, wherein the diodes comprise bothanodes and cathodes in an alternating pattern, wherein the conductive orsemi-conductive material is selected from the group consisting of:carbon, a carbon allotrope, an organic polymer, a metal, a metal alloy,an intermetallic material, a metallic glass, a composite material, apolymer, biocompatible material, or combinations thereof; and b) acurrent source.
 2. The electroluminescent cell of claim 1, furthercomprising wherein the shape of the three-dimensional post varies alongthe vertical axis.
 3. The electroluminescent cell of claim 1, furthercomprising wherein the cell provides energy conversion efficiency of atleast 10%.
 4. The electroluminescent cell of claim 1, further comprisingwherein the diode comprises a donor polymer and an acceptor polymer. 5.The electroluminescent cell of claim 4, further comprising wherein thedonor material combine with a hole.
 6. The electroluminescent cell ofclaim 1, further comprising wherein the anodes are selectively coatedwith the conductive polymer.
 7. The electroluminescent cell of claim 1,further comprising wherein the anodes are selectively coated withPEDOT:PSS.
 8. The electroluminescent cell of claim 1, further comprisingwherein the diodes are manufactured using a conductive orsemi-conductive material that is subjected to a patterning processfollowed by sintering, pyrolysis, or baking.
 9. The electroluminescentcell of claim 1, further comprising wherein the diodes are arranged in agrouped pattern.
 10. The electroluminescent cell of claim 1, furthercomprising wherein the diodes are arranged in a separated pattern. 11.The electroluminescent cell of claim 1, further comprising wherein thediodes are formed in a no trace architecture.
 12. The electroluminescentcell of claim 1, further comprising wherein the cell further comprises aprotective transparent material.
 13. The The electroluminescent cell ofclaim 1, wherein the microarray of three-dimensional diodes areconfigured on a single chip as an array selected from the groupconsisting of: a 5×5 array; a 10×10 array; a 30×30 array; a 50×50 array;a 75×75 array; a 100×100 array; a 200×200 array; a 250×250 array; a500×500 array; and a 750×750 array.
 14. The electroluminescent cell ofclaim 1, wherein the microarray of three-dimensional diodes areconfigured on a single chip as an array of posts having a spacingselected from the group consisting of about: 350 um; 150 um; 75 um; 50um; 20 um; 10 um; 1 um; and 0.5 um.
 15. The electroluminescent cell ofclaim 1, wherein the three-dimensional diodes have a diameter of atleast 150 um and a height that is greater than the diameter.
 16. Theelectroluminescent cell of claim 1, wherein the uniform spacing of thethree-dimensional diodes has a spacing of at least 350 um and a heightthat is greater than the spacing.
 17. The electroluminescent cell ofclaim 1, comprising wherein at least some of the three-dimensionaldiodes are in the shape of a cylindrical post, a pyramidal post, adiamond-shaped post, a spherical post, a hemispherical post, or arectangular post.
 18. The electroluminescent cell of claim 1, furthercomprising wherein the diodes are manufactured using a conductive orsemi-conductive material that is subjected to a patterning process.